Norbornadiene

Structural formula
General
Surname	Norbornadiene
other names	2,5-norbornadiene; Bicyclo [2.2.1] hepta-2,5-diene; Bicyclo [2.2.1] heptadiene;
Molecular formula	C 7 H 8
Brief description	light yellow liquid
External identifiers / databases
EC number	204-472-0
ECHA InfoCard	100.004.066
PubChem	8473
Wikidata	Q726795
properties
Molar mass	92.14 g mol −1
Physical state	liquid
density	0.91 g cm −3
Melting point	−19 ° C
boiling point	90 ° C
Vapor pressure	69 h Pa (20 ° C); 112 hPa (30 ° C); 172 hPa (40 ° C); 256 hPa (50 ° C);
solubility	practically insoluble in water
Refractive index	1.470 (20 ° C)
safety instructions
GHS labeling of hazardous substances danger
H and P phrases	H: 225
	P: 210-403 + 235
Toxicological data	3,850 mg kg −1 ( LD 50 , rat , oral )
	As far as possible and customary, SI units are used. Unless otherwise noted, the data given apply to standard conditions . Refractive index: Na-D line , 20 ° C

Norbornadiene is a bicyclic hydrocarbon that is being discussed as a potential candidate for storing solar energy . It is also of interest as a metal ligand that is used in homogeneous catalysis . Norbornadiene is also a useful dienophile in the Diels-Alder reaction . Related bicyclic compounds are norbornene , which has the same carbon structure but only one double bond, and norbornane , also with the same structure, but without double bonds and thus saturated.

synthesis

Norbornadiene can be produced by the reaction of cyclopentadiene and acetylene .

properties

Norbornadiene forms highly flammable vapor-air mixtures. The compound has a flash point of around −11 ° C. The explosion range is between 1% by volume (38 g / m ³ ) as the lower explosion limit (LEL) and 6.3% by volume as the upper explosion limit (UEL). The ignition temperature is 350 ° C. The substance therefore falls into temperature class T2.

Storage of solar energy

Quadricyclane , a valence isomer , can be obtained by photochemical isomerization in the presence of a sensitizer such as e.g. B. Michler's ketone or acetophenone can be obtained.

Reaction of norbornadiene to quadricyclane:
forward reaction by supplying energy from light h · ν and reverse reaction by increasing the temperature Δ

This pair of isomers is of potential interest for the storage of solar energy if the reverse reaction is possible through a controlled process. Theoretically storable energy is −89 kJ / mol. Since the main absorption of this reaction is around 300 nm, but only small portions of the sunlight are below 400 nm, this use is limited.

Reactions

Norbornadiene is a reactive reagent in cycloadditions and also a starting material for the production of diamond and sumanes . It is also used as an acetylene transfer agent in reactions with tetrazines such as 3,6-di-2-pyridyl-1,2,4,5-tetrazine .

Use as a ligand

Norbornadiene is a versatile ligand in organometallic chemistry where it acts as a two- or four- electron donor .

An example of this is tetracarbonyl (norbornadiene) chromium (0).

literature

Beyer / Walter : Textbook of Organic Chemistry , 19th edition, S. Hirzel Verlag, Stuttgart 1981, ISBN 3-7776-0356-2 , p. 390.
Streitwieser / Heathcock : Organic Chemistry , 1st edition, Verlag Chemie, Weinheim 1980, ISBN 3-527-25810-8 , pp. 1351-1352.

Web links

Commons : Norbornadien - collection of images, videos and audio files

Individual evidence

↑ ^a ^b ^c data sheet bicyclo [2.2.1] hepta-2,5-diene, 98% from Sigma-Aldrich , accessed on March 13, 2014 ( PDF ).
↑ ^a ^b ^c ^d ^e ^f ^g ^h ⁱ ^j ^k ^l ^m Entry on bicycloheptadiene in the GESTIS substance database of the IFA , accessed on November 28, 2017(JavaScript required) .
↑ ^a ^b ^c ^d ^e Entry on Norborna-2,5-diene. In: Römpp Online . Georg Thieme Verlag, accessed on November 28, 2017.
↑ Claibourne D. Smith: Quadricyclane In: Organic Synthesis . 51, 1971, p. 133, doi : 10.15227 / orgsyn.051.0133 ; Coll. Vol. 6, 1988, p. 962 ( PDF ).
↑ AD Dubonosov, Vladimir A. Bren, VA Chernoivanov: Norbornadienes - quadricyclane as to abiotic system for the storage of solar energy. In: Russian Chemical Reviews 71 (2002): 917-927.
↑ Gregory W. Sluggett, Nicholas J. Turro, Heinz D. Roth: Rh (III) -Photosensitized interconversion of norbornadiene and Quadricyclane . In: J. Phys. Chem. A . 101, No. 47, 1997, pp. 8834-8838. doi : 10.1021 / jp972007h .
↑ Constantine Philippopoulos, Dimitrios Economou, Constantine Economou, John Marangozis: Norbornadiene-Quadricyclane System in the Photochemical Conversion and Storage of Solar Energy . In: Ind. Eng. Chem. Res . 22, No. 4, 1983, p. 627. doi : 10.1021 / i300012a021 .
↑ Tamara M. Gund, Wilfried Thielecke, Paul v. R. Schleyer: Diamantane In: Organic Syntheses . 53, 1973, p. 30, doi : 10.15227 / orgsyn.053.0030 ; Coll. Vol. 6, 1988, p. 378 ( PDF ).
↑ Ronald N. Warrener, Peter A. Harrison: π-Bond Screening in Benzonorbornadienes: The Role of 7-Substituents in Governing the Facial Selectivity for the Diels-Alder Reaction of Benzonorbornadienes with 3,6-Di (2-pyridyl) -s -Tetrazine . In: Molecules . 6, No. 4, 2001, pp. 353-369. doi : 10.3390 / 60400353 .
↑ Ryo Shintani, Tamio Hayashi: Chiral Diene Ligands for Asymmetric Catalysis , Aldrichimica Acta , 2009, vol. 42, number 2, pp. 31-38.
↑ Markus Strotmann, Rudolf Wartchow, Holger Butenschön: High yield synthesis and structures of some achiral and chiral (diphosphine) tetracarbonylchromium (0) chelate complexes with tetracarbonyl (norbornadiene) chromium (0) as complexation reagent . In: Arkivoc . 2004, pp. KK-1112F.

[Sigma-1] ta sheet bicyclo [2.2.1] hepta-2,5-diene, 98% from Sigma-Aldrich , accessed on March 13, 2014 ( PDF ).

[GESTIS-2] ↑ ^a ^b ^c ^d ^e ^f ^g ^h ⁱ ^j ^k ^l ^m Entry on bicycloheptadiene in the GESTIS substance database of the IFA , accessed on November 28, 2017(JavaScript required) .

[Roempp-3] Entry on Norborna-2,5-diene. In: Römpp Online . Georg Thieme Verlag, accessed on November 28, 2017.

[orgsyn_1-4] Claibourne D. Smith: Quadricyclane In: Organic Synthesis . 51, 1971, p. 133, doi : 10.15227 / orgsyn.051.0133 ; Coll. Vol. 6, 1988, p. 962 ( PDF ).

[5] AD Dubonosov, Vladimir A. Bren, VA Chernoivanov: Norbornadienes - quadricyclane as to abiotic system for the storage of solar energy. In: Russian Chemical Reviews 71 (2002): 917-927.

[6] Gregory W. Sluggett, Nicholas J. Turro, Heinz D. Roth: Rh (III) -Photosensitized interconversion of norbornadiene and Quadricyclane . In: J. Phys. Chem. A . 101, No. 47, 1997, pp. 8834-8838. doi : 10.1021 / jp972007h .

[7] Constantine Philippopoulos, Dimitrios Economou, Constantine Economou, John Marangozis: Norbornadiene-Quadricyclane System in the Photochemical Conversion and Storage of Solar Energy . In: Ind. Eng. Chem. Res . 22, No. 4, 1983, p. 627. doi : 10.1021 / i300012a021 .

[orgsyn_2-8] Tamara M. Gund, Wilfried Thielecke, Paul v. R. Schleyer: Diamantane In: Organic Syntheses . 53, 1973, p. 30, doi : 10.15227 / orgsyn.053.0030 ; Coll. Vol. 6, 1988, p. 378 ( PDF ).

[9] Ronald N. Warrener, Peter A. Harrison: π-Bond Screening in Benzonorbornadienes: The Role of 7-Substituents in Governing the Facial Selectivity for the Diels-Alder Reaction of Benzonorbornadienes with 3,6-Di (2-pyridyl) -s -Tetrazine . In: Molecules . 6, No. 4, 2001, pp. 353-369. doi : 10.3390 / 60400353 .

[10] Ryo Shintani, Tamio Hayashi: Chiral Diene Ligands for Asymmetric Catalysis , Aldrichimica Acta , 2009, vol. 42, number 2, pp. 31-38.

[11] Markus Strotmann, Rudolf Wartchow, Holger Butenschön: High yield synthesis and structures of some achiral and chiral (diphosphine) tetracarbonylchromium (0) chelate complexes with tetracarbonyl (norbornadiene) chromium (0) as complexation reagent . In: Arkivoc . 2004, pp. KK-1112F.